Subresinous esterification derivatives of hydroxylated acylated diamides and method of making same



Patented Sept. 4, 1945 scnmsmo s" ESTERIFICATION DERIVA TVIVES F HYDROXYLATED ACYLATED DIAMIDES VANDI METHOD or ff iiiivinlne oibote, University City, and Bernhard Keiser, :Webster -Groves, Mo., assignors to p 1 Petrolite Corporation, Ltd., Wilmington, Del., a' "corporation-of Delaware V I NqDratiigirig. Original application] une 15; 1942 Serial No. 447,166. Divided and this application j f Angust 2; 1Q43,'Serial No. 497,133

- This invention relates to a; new chenncal prod-f uct or composition of matter, our'pres'ent application beingga division of our co-pending application Serial No: '44'7,1 66,"flled June" 15, 1942, which subsequentlymatured as U. S. Patent No'. 2,353,709, dated'July 1a,;1944r a The mainflobject. of our invention is to providea new chemical p'rqductor compound that is particularly adapted'ior use' a s a demulsifier in the resolution or crude oil emulsions. "-"Another object of our invention is to provide a practicable method for anufacturingsaid new chemical product or compound.

'Althoughio'ne' of thepliimary; objects 'of our invention is to provide a new compo'undor'composition of matter that" isan efficient demuls'ifier for crude oil emulsions of the water-in oil' type; the said cbmpound or c'omposition'of matter is adaptedffor'usein'other' arts; as hereinafter ini -F-yux;w w

We have discovered that if one 'oxyalkylates glycerol 'so as tdintroduce at least-three oxyal kyle'ne fradicals for "each: hydroxyl group, and if the-"product so 'obtained is reacted with'a polybasic carb'oxy acid'having not over eight carbon atoms; and in su'ch mann'er as to yield a fractional ester, due tothefpresence of at least one free carboxyl radical, one can' then ester ify said acidic If treated with an oxyalkylating agent, and momentarili consideration will be limited to an oxyethylating agent, one may obtain an oxyethylbasic carboxy acid i-may-beindicated by the foilmaterial-or intermediate product withat least one mole of an alcoholic compound of the type hereindescrlbed to give a variety of new compositions of matter which have utility in various arts, and particularly in the demuls'ificat'ion of crude oil.

The compounds herein contemplated maybe produced in any suitable manner, but are usually manufactured by'- following one oi twogeneral procedures. "In one'o'f said procedures the oxyalv k-ylated glycerol,"which is, in essence, a polyhydric alcohol; is reacted with a pol-ybasic acid so as to give an acidic material or intermediateproduct, which,in turn, is reacted with'aln alcoholic body of the kind hereinafter described, and momentarily indicated by" the formula R1 (OH) m'.{ 1 Generically,

the-alcoholicbody-herein contemplated maybe considered a. member of theclass in which m may vary from '1 tom, although the specific s'ignificance' of m in the present instance will be hereinafterindicated. The second procedure is to react an alcohol of the formula type -R1(oH) m with a polybasic acid so as to produce an intermediate product, and then react said intermediate product onfraetional ester with the selected oxyalkylated lycerol; Q

-Glycerol may'beconveniently indicated by the following formular I 4 ""11. I/OHV l nkin which ni'has the value of on e or twoll Simi larly if two molesof the polybasic acid be. used, thenjhe compound maybe indicatedby the followingformula: H p

- Q H'QJ QQIHQQ HM t ""fi imqz 'eif. Lilgewise, ifthre'eTmoles off a; polybasic acid are employed, the compound may be indicated by the following iorrnula': f1 p p v i I f; (ciaioo oocewocrow f c CHiQm(CiHi0)fi' O KIO HMQ I v o,Hio);. ooomotion i j If a fractionalie'ster oi. the'hind exemplified by the three precedingffonnu'la's in reacted with one or more moles of'an' alcohol ofthe kind' previously described in a genericfsense as RMOHm, then obviously, one may obtain amaterial of the type i'n' whichmisro ltor .2 1J=1is:0,-,110r;2, and z is 1, 2 orBgandimfiisiIorj;andyislorz. a

It has-been; preriouslystated that compounds of the type herein contemplated-may heobtained by oxyalkylatingr agents, with4:mt being limited to ethyleneroxide. Suitableoxyalkylating agents-inelude; ethylene. oxide, propylene oxide, butylene 1 oxideand zlycid; w ich. a u h not n lud oxide.

strictly speak-inggby the, unitary. structure CnHgnQ, is included within-the meaning'of the hereto ap pended claims and may be simply considered asa variant of propylene oxide, 1. e hydroxypropylene ammonium radical, or substituted ammonium rad- Similarly, where aoarboxylichydrogen atom appears, it may be replaced by:metal, an

ical, or by an organic group derived from an alco.. hol, such as an aliphatic alcohol an aralkyl alcohol, or an alicyclic alcoholf lt m'ay also beconv verted into an amide, including a po'lyamino- 1' amide. Thus, the preceding formula may be re written in its broader scope,-

-follows:- c

ucnnton oocmcoomu'lr if in which n replaces the numbers 2, 3 or 4, z includes the acidic hydrogen atom itself. In the above formula, and hereafter for convenience, R1 is intended to includeany hydroxyl groups that remain. c I

If the compounds herein contemplated are "btain'ed'under usualfcondi,tio ns, at the lowest 'temperatures, then the monomeric form'is most likely to result.

The production of the compounds herein contemplated is the result ofone or more esterification steps. As is well known, esterification procedures can be carried out in .various: manners, but generally speaking, :esterifications can be carriedout at the lowest fe'asible temperatures by using one or several procedures; One procedure is to pass an inert dried gas through the mass to be esterified, andhavepresent at the same time a small amount of a catalyst, such as dried HCl gas, a dried sulfonic acid, or the like. Anotherjand'b'etter procedure, in many instances, is ,td'em'ploythevapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such'a manner as to trap out the water and return the liquid to the reacting vessel. This procedure is. commonly employed in the arts, and for convenience, reference is made. to U. S. Patent No." 2,264 '759, dated December 2,1941, to Paul C. Jones. jj

Referring again to the last 'two' formulas indicating the compounds under consideration, it can be readily understood that such compounds, in numerous instances, have the property of polyfunctionality. Inview of this ,fact, where there is atleast one residual carboxyl and at least one residual hydroxyl, one would expect'that under suitable conditions, instead of obtaining the monomeric compounds indicated, one would in reality obtain a polymer in the sense, for exam ple, that polyethylene glycols represent a polymer of ethylene glycol. quently used to indicate the polymerized product derived from, a monomer in which the polymer has the same identical composition as the monomer. polymerization involves the splitting and loss of water so that the process is essentially, selfesterification. -Thus, strictly speaking, the polymeric' compounds are not absolutely. isomers of esterification products"oi the monomeric compounds.

In view of what has been said, and in view of the recognized hydrophile properties of the recurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through self-emulsifying oils, to materials which are balsam-like andsub-resinous or semi-resinous in nature. Th compounds may vary from monomers to polymers, in which the unitary structure ap- ".pears'anumber of times, for instance, 10 or 12 times. It is .to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In ,other words the polymerized compounds arev soluble. to a fairly definite extent, for instance, at least 5% in some solvents, "such as water, alcohol, benzene; dichloroethyl ether, acetone,"cresylicv acid, acetic acid, ethyl acetate, dioxane, orflthe like. This is simply another waybf st'ating,tha.t thepolymerized product contemplated must be of the subresinous type,'which is commonly referred to as an A resin, or a B resin, as distinguished from a C resin, which is a highly infusible,' insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq.).' i f Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither afree 'hydroxyl nor a free carboxyl group, and one may also obtain a compound of the typein which there is present at least one free carboxyl, or at least, one

, free' hydroxyl, or both.' The word polar? has sometimes been used in the arts inthisparticuatom equivalent, such, for examplaas a metal,

an ammonium radical, a substituted ammonium radical, etc. In the hereto appendedclaims the word polar is used this specific sense.

We are aware thatcdmpounds similar to those contemplated inthe present instance may be derived from polyhydroxylated .compoundshaving more than three hydroxyl groups; For instance,

. they may be derived from acyclic ,diglycerol, .tri-

glycerol, tetraglycerol, mixed 'polyglycerols, mannitol, sorbitol, various hexitols, .dulcitol, pentaerythritol, sorbitan, mannitan,dipentaerythritol monoether, and other similar;- compounds. Such particular types in which higher hydroxylated The term "polar" is frei In the present instance, however,

materials are subjected to oxyalkylation and then employed in the same manner as oxyalkylated glycerol, is employed in the present, instance, are not contemplatedin this specific case, although attention is directedto thesame. 1 7

Reference is also made to other oxyalkylated compounds which maybe used as reactants to replace oxyalkylated jglycerol, oroxyalkylated ethylene glycohwhich latter reactant is described inan application hereinafter referred to, to wit,

' Serial No. 401,384,'-filed July; 7,;194 1, which subsethe monomeric compounds, but-since, for all practical purposes, they can bEfSO indicated, and

quently matured as U." S,- Patent No. 2,324,494., dated July 20, 1943. The reactants thus contemplated include the type inwhich therejs an amino or amido nitrogen atom, particularly when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials'including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups.- .For instance; the oxyalkylated derivatives, particularly the oxy+ ethylated derivatives of 'ethyldiethanolamine, bis(hydroxyethyl)acetamide, .ithe acetamidemof tris.(hydroxymethyl) aminomethane, :1;- tetrahy droxylated ethylene diamine, etc. Compounds may alsobe derived from cyclic diglycerol sand the like. 1

Furthermore, for, convenience,. attention is .directed .to a somewhat similanclasszof materials which: are described in .our application Serial N 0. 401,384, filed July 7,. 1941, which subsequently matured as U. S. Patent No.:Z,324,494,'-dated July 20, 1943. Said application involyesthe use of. the same type of alcoholic bodies for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for instance, involving theintroduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or' more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the. type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutari'c, 'adipic, maleic, and phthalic. Similarly, one may employ acids-such as 'fumaric, 'glutaconic, andvar'ious' others, such as citric, maleic, tartaric, and the like: The selec tion of the particular tribasic ordibasic acid employed, is usually concerned largely- .with the convenience of manufacture of the nnis'hed ester, and ,also the price of the reactants. Generally speaking, phthalic acid or anhydride tendstopror duce resinous materials, and greater .care 1 must be'employed if the ultimate or f nal product of. a sub-resinous type, specifically, the preferred type [of polyba'sic acid is such as tocontainsix carbon atoms or 1 less. Generally speaking; the higher thetemperatur'e employed, the easier it is to obtain large yields. of esterified pr duct al though polymerization may be stimulated. Oxalic acid may be comparatively cheap. but it clecom poses readily at slightly above the boiling point of water. For this reason, it is more desirable to use'a'n acid which is more resistant to pyrolysis. Similarly, when a poly-basic acid is. available in the form of an anhydride, such anhydride is apt to produce the ester withgreater-ease thanthe acid itself.v For this reason, maleic anhydride is particularly adaptable, andalso, everything else considered, the costis comparatively low on a per molar-basis, even though somewhathigher on a per pound basis. Succinic acid or the anhydride has many attractive qualities 'of maleic anhydricle, arldthis is also true of adipic acid. .Eor

purpose of brevity, the bulkofthe examples, hereinafter illustrated, .will referto the use of maleic anhydride, although it is understood that any othersuitable polybasicacid may "be employed. Furthermora reference is madetoderivatives obtained by oxyethylation, although, .asupreviously pointed out, other oxyalkylatingagentstmaybe employed. 7 i As far as the. rangeiof oxyethylated 'glycerols employed as reactants is concerned, it is our preference to employ those in'ewhich approximately 15 to 24 oxyethylene groups have-been introduced into a single glycerol molecule. This means that approximately. five to eightoxyethylene radicals have been introduced for each original hydroxyl glOllD. I a? I :fi-

,Theoxyalkylation of glycerol'is a well-known procedure (see Example 11 f German Patent No. 605,973, dated November 22, '1934,"-to IsG. Farbe'n industrie A. G.). V The procedureindicated in the followingthree example's'is substantially identical weight, of caustic soda solution having a specific ill gravityof 1.383. The caustic-soda-acts as a ceta lyst.=- The ethylene "oxide-is addedin relatively small amounts, for instance, about 44 'pounds='at a- 'time; Thetem-perature employed isf'romJSO- 180 C. Generally speaking,- the gauge-pressure during the operation approximates 200-pounds at the maximum, and when" reaction is complete, drops tolzero, due to complete absorptionof the ethylene oxide; 11 Wh'en; all the ethylene oxide has been absorbed and the reactants cooled; a second small-portionpfor instance, 4e; more-pounds of ethylene oxide, are added andthe procedure re peated until the desired ratio of 15 pound moles orethylene oxide tofone poundmole of glycei'o'l is obtained This represents 660 pounds of ethylene oxid'for 92 pounds of-glycerol.-

" QOxxErnxiA rsn GhYCllROh 'Examplaz Y'I he ratio of ethylene oxide is increased to21 pound 'moles'for each poundmo'le of glycerol. Otherwise, the same procedure is followed as'in Example 1, precedingj" QxyEr L rni) GLycnRo E 3 Thei'same. procedure is followed as in t two previous examples, except that the ratio of ethylene oxideto glycerol is increased to2l 1. 1 OXYETHYLATEDCILYCEROL MALEATE w e l pound mole of oxyethylated glyceroli 'fl tojl5 ratio) prepared in the; manner previously. do; scribedis treated with one pound moleotma'leic anhydride and heated at approximately-1109 0,; for approximately thirty minutes to tworhours, with constant; stirring, so as; to yield a monomaleatei 7 ff Ox srHYLArEn GLyonRoL MAr mrn i 1. The same 'procedure is followed as'in the *pre ceding example, except that two moles of maliel'c anhydride are employed so as to obtain the dimaleate instead or the .monomaleate. 4 Oxysrnyrixrsn GLyc RoL MArEA'ri: V. @Examplci- The-same procedure is followed as in-"thetwo preceding examples, except'that three moles of maleic -anhydride are employed so as to-obtairi thetrimflleate. .7 I {,ffOiQYl T-THYILATED GLxonaoL MAI isAlre'. v ,1 Examples! fIh'e same procedure is employed as in the pref ceding examples, exceptthat oxyethy'lated glyc erol '(ratio Ltd 18') is substituted in place of oxy ethylated glycerol (ratio 1 to 15). I I "LO xy rHYLATED Greener MALEATE.

Example The same procedure is employed as in the pre' ceding examples, except that 'ox'yethylated glyc; e'r' ol t-ratio l -to 21) is employed instead of oxy ethylatd glycerol (ratio '1 to 15) 01 (1 13018)? the formula R1(OH)m. The sub-generic class of alcoholic compounds employed as reactants in the manufacture of the present compounds, are hydroxylated acylated diamides containing: (a)

an acyl radicalderived from a polybasic carboxy acid having not more than 6 carbon atoms, and the acyl radical thereof linked to two amino nitrogen atoms; (b) an acyl radical derived from a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atoms; and (c) an alcoholi-form hydroxyl radical.

Detergent-iorming acids having at least 8 and not more than 32 carbon atoms are exemplified by fatty-acids, naphthenic acids, abietic acids, oxidized paraffin or wax acids, or the, like, or by simple modifications thereof, which do not detract from the ability of the acid to combine with alkali to produce soap or soap-like materials. As to oxidized petroleum acids, see U. S. Patent No. 2,242,837, dated May 20, 1941, to Shields.

Thus, hydrogenated oleic acid, chlorinated naphthenic acid, or brominated abietic acid will form such detergent-forming bodies with the same ease'as the parent materials, themselves. The oxidized acids obtained by blowing or oxidation of the acids or esters, are satisfactory. Such acids have frequently been referred ,to collectively in the art as monocarboxy' detergentforming acids. Needless to say, the acylation need not be conducted by means of the acid itself, but may be conducted by means of any compound of the acid which contains the acid radical; for instance, an ester, an amide, an anhydride, an acyl chloride, etc. It'is our preference to use the fatty acids as the most desirable form of a detergent-forming acid, and particularly the unsaturated fatty acids, for instance, ricinoleic acid, oleic acid, mixed fatty acids derived from soyabean oil, rapeseed oil, sesame oil, cottonseed oil, corn oil, peanut oil, and the like. Fatty acids such as lauric acid, myristic acid, palmitic acid, and the like, may be employed. 7

. The polybasic carboxy acids which may be employed include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tricarballylic acid, fumaric acid, maleic acid, aconitic acid, malic acid, tartaric acid, citric acid, etc. Such acids may be conveniently referred to as low molal polybasic carboxy. acids, or, more preferably, low molal acids;

In-regard to both the detergent-forming acids and in regard to the low molal acids, it is obvious thatsone need not use the acid itself as areactant, but may use some suitable derivative, such as the acyl chloride, the anhydride, the ester, or amide; i. e., any suitable form may be used which is the functional equivalent in supplying the acyl radical. Suitable primary and secondary amines which may be used as primary reactants include the following hydroxylated types: Diethanolamine, monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dipropanolamine,

'propyl propanolamine, etc. 7 Other examples includes cyclohexylolamine, dicyclohexylolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzylethanolamine, benzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine, octadecylethanolamine, cyclohexanolethanolamine, etc. U v I If the low molal polycarboxy acid happensto beihydroxylated, as in the instance of tartaric acid, citric acid, hydroxysuccinic acid, and the like, it is obvious that a hydroxylated detergentforming acid, for instance, ricinoleic acid, hydroxystearic acid, and the like, could be esterified therewith, i. e., with the hydroxyl group which is part of the low molal acyl radical; and under such circumstances, the primary or secondary amine need not be hydroxylated. Under these circumstances, one might employ compounds such as amylamine, diamylamine, butylamine, dibutylamine, benzylamine, cyclohexylamine, etc.

Other suitable types of amines will be described subsequently. For instance, one may employ the type involving the presence of an ether linkage,

as, for example, the following:

Subsequently, reference will be made'to U. S. Patent No. 2,238,929, dated April 22, 1941, to Cahn and Harris. Momentarily attention is directed to the numerous amino compounds, particularly secondary hydroxylated amines there described.

Such additional amino compounds are suitable as In the aforementioned Cahn and Harris patent there is described certain materials which'are employed in the manufacture of new compounds of the kind'specifically contemplated in said Cahn and Harris patent. Said compounds are derived both from low molal monocarboxy acids and low molal polybasic carboxy acids. It may be well to illustrate both types, in order to understand clearly the manufacture of the intermediate products for use in obtaining the compositions of matter herein contemplated, and particularly when manufactured for use as demulsifiers of water-in-oil emulsions.

Example A, part 1 of the aforementioned Cahn and Harris patent will serve excellently as an initial illustration and is as follows:

Example A (l) 224 grams of methyl acetate (3 moles) and 210 grams of diethanolamine (2 moles) were mixed together, two layers forming at first, the mixture becoming a homogeneous mass after a short time. The mixture was refluxed for 19 hours, at which time of the diethanolamine had reacted. A portion of the reaction mixture was subjected to a vacuum of 6 millimeters at 60 degrees C. in order to drive oil the volatile material, namely, the unreacted methyl acetate and the methyl alcohol which was formed during the reaction. The residue, upon titration, showed a content of 4.64% of free diethanolamine. To 192.5 grams of this residue, 34.7 grams of methyl acetate were added and the mixture was refluxed for 3 hours. The resulting reaction product was then freed from its low boiling constituents, namely, the methyl alcohol and unreacted methyl acetate, by maintaining the mass at '70 degrees C. under a pressure of 6 millimeters. The residue contained approximately 0.8% of unreacted diethanolamine, basedupon a determination of the alkalinity of said residue by titration. The product was a light yellow colored syrup, soluble in water, and contained a compound which was essentially the acetic acid amide of diethanolamine, having the following formula:

'oin orr CH:ON

Having obtained a material of the kind above described, it is obvious'that one can then esterify the material with either one or two moles of a detergent-forming 'monocarboxy acid, so as. te obtain a hydroxylated derivative. Obviously, if the detergent-forming acid employed does not contain an alcoholic hydroxyl radical, for instance, if it is of the type other than exemplified by ricinoleic acid, hydroxystearic acid, and the like, then one can only esterify one mole of such detergent-forming acid with a compound of the kind above described, for the reason that there must be a residual alcoholiiorm hydroxyl radical. If, however, an acid such as ricinoleic acid, hydroxystearic acid, or the like is employed, then, of course, two moles of such detergent-forming acid can be employed. Similarly, if desired, one might esterify one hydroxyl with oleic acid, and the other hydroxyl with ricinoleic acid.

' Ii the experiment above described is repeated, using monoethanolamine in the equivalent amount, then the final product is characterized by the following formula:

oiHioH CH:CN

The limitations in regard to the above type of compound is perfectly obvious. Unless one can produce a secondary amide, which is difiicult, and

generally speaking, not particularly feasible, one must, of necessity, esterify with a hydroxylated detergent-forming acid, such as ricinoleic acid, hydroxystearic acid, or the like.

If, however, instead of using acetic acid, one

uses lactic acid or some other hydroxylated low molal carboxy acid, such as hydroxyacetic acid, then the two formulas above described change to the following formula:

' CIHAOH OHCH2CN O C:H4OH

OHCH:C-N

0 The presence of this additional hydroxyl ofiers additional opportunity for reaction, and further elaboration is not necessary, except perhaps, to

point out that even a type of material such as droxymethyl)aminomethane, or similar types of compounds, such as an amide oi the following type, which may be used for reaction with a detergent-forming acid:

tioned Cahn and Harris patent, insofar that it illustrates a large number of intermediate products which may be utilized to produce various final compositions of matter, as for example, sulfated orsulionatedderivatives, as contemplated in said arorexnention'ed U. S. Patent No. 2,238,929. However, theintermediate materials there described obviously can be used as alcoholic bodies in the preparation of compounds of the type herein contemplated. Such materials as there described are largely derivatives of hydroxylated secondary amines; but for the purposes herein contemplated, such limitation does not exist, in view ofwhat has already been said. In the present instance, however, one is concerned with derivatives obtained from low molal polybasic carboxy acids of the kind described; and it is to be noted that, although many illustrations inthe aforementioned Cahn and Harrisv patent are concerned withlow molal monocarboxy acids, the corresponding low molal polybasic carboxy acid compound is readily obtainable, all of which will be obvious, in view of what'is said subsequently;

The following is substantially "the manufacturing procedure set forth in the Cahn and-Harris patent, and which has been quoted in detail under the item previously identified as Example A, part '1:

Gne canemploy one pound'mole of diethyl oxalate and two pound moles of monoethanolamine and react these compounds in'a similar manner. This procedure yields a corresponding diamide of oxalic acid, along with the liberation of two pound moles of ethyl. alcohol. Such bis- (hydroxyethyDoxalic acid diamide may be reacted with ricinoleic acid inthe ratio of one pound mole of the diamide'for 2 pound moles of ricinoleic acid. Similarly, a product can be obtained employing only one mole of ricinoleic acid for one mole of the diamide; or one might employ one mole of oleic acid and one mole of ricinoleic acid for; each mole of, thediamide. Similarly, diethanolamine may be employed with, diethyl oxalate to give the corresponding tetra(hydroxyethyl) oxalic acid diamide' Instead of diethyl oxalate, diethyl maleate, or numerous other reactants can be employed. Attention is called to the fact that hydroxylated polybasic carboxy acids might. be employed in the same'manner as hydroxyacetic acid can be employed in the. analogous type of compound where a low molal monocarboxyacid is used;

By way of illustration, the following examples will serve:

IIYDROXYLATED D smal: T PE INTERMEDIATE Example 1 v, One pound mole of a diamide of the following formula: v

H 0 0 H N l N, oHGiHi oiuion is esteruied with one pound mole of ricinoleic acid until esterification is complete. Such esterificaticn reaction can be conducted by any one of the conventional means, usually heating. at a temperature above the boiling point of water; for instance, 116- 160 C. is sufflcient. In some cases it may be desirable to pass a dried inert gas through the reactingmass, as, for example, dried carbon dioxide or dried nitrogen. Sometimes the reaction is extended by the presence of a small amountof a sulfonic acid as a catalyst, for instance, /2% of toluene sulfonic acid. In other instances, esterifi'cati'on maybe conducted in the 6 presence of an inert solvent, 'such as xylene, which is permitted to distil off, carrying-water vapor with it. The vapors are condensed, separation of water and xylene permitted to take place} and the xylene returned to the reacting vesselwhile-the water is diverted to a'suita ble' draw-off connection; HEDROXYLATEDDIAMIEE TYPE; I TERM DIATE I ,gExamp le 2 I One pound mole of'oleic acid issubst'ituted for one pound -mole of'the- 'ricinoleic acid in the preceding example. 7

LH DR XYLATEE DIAii/IIEE TY E INTERMEDIATE p Example 3 One pound mole of naphthenic acid is substituted for riclnoleic acid in Example 1, preceding. HYnRoxvLATEn DIA IEE TYPE INTERMEDIATE Examples! I Two pound moles of ricinoleic acid are' substituted'for one pound mole ofricinoleic acid in Example 1, preceding.

HYnRox L TEn DIAMInE TYPE IN ERMEDIATE I I Example 5 I One pound mole of oleic acid and one pound mole of ricinoleic acid are substituted for one pound mole of ricinoleic acid are substituted for onepound mole of rlcinoleic acid in Example 1, preceding. H

DIAMIDE TYPE INTERMEDIATE Example 6 4 The diamide derivedfrom diethanolamine and diethyl oxalate of the following composition:

oncinl 0' o cznlon 11 ll- NC-C+ N qlnion HYIJRoxYLATEo is substituted for the amide in Examples 1-5,

preceding. I V

.- HvnRoxYLATEn VDQIAMIJDLE TYPE INTER EDIATE Example 7 One poundmole of diethyl oxalate is reacted with onepound mole of monoethanolamine and one pound mole ofdiethanolamine to give a mixture containing some diamidesof the type de scribed in the preceding examples, and also having present an appreciable amount of a diamide of the following composition:

described in Examples 1-7, preceding.

I HYDROXYL'ATED' DIA IEE TYPE INTERMEDIATE 7 Example? One pound mole of. diethyl'oxalate is reacted with tris(hydroxymethyl) aminomethane to give a diamide of the following composition:

- o --ll H- man-050E031);

, O 1 H I! (OHCH2):4EC N +C Such dlamideis substituted in the previous examples, such as 1-5, inclusive.

HYER'QXYLATEE DIAM IDE' TYP IrrrExivi D ATis; f f

Diethyl maleate is substituted: for diethyl oxalate in Examples 1-9, preceding.

,COIVIPLETED MONOMERIC D IV TIV r mp l One pound-mole ofa productof the kind described under the heading Oxyethylated glycerol maleate, Example 1is-reacted with one pound mole of fHydroxylated diamide type intermediate, Example 1 preferably in theabsence of any: high boiling hydrocarbon "or inert solvent. Howevenif an inert vaporizing solvent is'employed, it is gen= erallynecessary to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difliculty. In otherinstances, however, such high boiling inert vaporizing solvent, if employed, might be permitted to remain in the reacted'mass and appear as a constituent or ingredient of the final product. In any event, our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceedwith the elimination of water. The temperature of reaction is about to 200? C. and time of reactionzabout 20 hours.

' "COMPLETED MoNo ERIc DERIv T v Example 2 The same procedure is followed as in Completed monomeric derivative, Example 1, preceding, except that the dirmaleate described under the heading Oxyethylatedglycerol maleate, Example 2 is used instead of the monomaleate.

VCOMPLETEP MONOMERIC DERIV TIVE I Example 7 I L The same procedure'is followed as in the two preceding examples} except that the trimaleate is substituted for themonomaleate or dimaleate in thetwc preceding examples.

V COMPLETEDlMONOll/[ERIQ DERIVATIVE Examples I Y Y The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the maleate, or each pound mole of the trimaleate, instead of using one pound mole of a hydroxylated diamide of the kind employed in Examples I to 3, preceding, as a reactant, one employs two pound moles.

COMPLETED MONOMERIC DERIVATIVE V 'Examplefi I Thesame procedureis followed as, in Example 3, precedingexcept that for each pound mole of trimaleate, instead of adding one pound 'niole of a hydroxylated diamide of the kind employed in Examples 1 to 3, preceding, one'adds three pound moles of a hydroxylated diamide of the kind employed in Examples 1 to 3, for reaction.

COMPLETED MONOMERIC DERIVATIVE Example 7 The same procedure is followed as in Example ample, one indicated by the ratio of 1 to 21.

(See Oxyethylated glycerol maleate', Example 5, preceding.) I V COMPLETED. MONOMERIC DERIVATIVE Example 8 The same procedure is followed as in Examples 1 to 7, preceding, except that the hydroxylated diamide employed is of the type exemplifiedby Hydroxylated type intermediate, Example 5.

COMPLETED MoNoMERro DERIVATIVE 7 Example 9 I The same procedure is followed as in Examples 1 to-7, preceding, except that the hydroxylated diamide employed is of the type exemplified by "Hydroxylated type intermediate, Example '7.

'CoMPLErEn Monomsnrc DERIVATIVE Example 10 The same procedure is followed as in Examples l (30 7', preceding, except that the hydroxylated .diamide employed is of the type exemplified by Hydroxylated type intermediate, Examplefl.

The method of producing such fractionalesters is well known. The general procedure is to employ a temperature above the boiling'point of water and below the 'pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esterification step. If desired, an inert gas, such as dried nitrogen or dried carbon dioxide, may be passed through themixture. Sometimes it is desirable to add an esterification catalyst, such as sulfuricacid; benzene sulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. (See U. S. Patent No. 2,075,l0'7, dated March '30, 1937, to Frasier.)

Sometimes esterification is conducted most readily in the presence of an inert solvent that carries away the water of esterification which may be formed. although as is readily appreciated, such water of esterifi'cation is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol; water is formed, for instance; when citric acid is employed, then a solvent such as xylene may be present and employed to carryoff the water formed. The mixture of xylene vapors and water vapors can be condensed. so that the water is .separated. -The xylene is then returned to the reaction vesselfor further circulation. This is a conventional and well known procedure and requires no further elaboration.

In the previous monomeric examples there-is a definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organicreactions of this kind, and as is well known, organic reactions per se are characterized by'the fact that 100% yields are the exception, rather than the rule, and that significant yields are satis factory, especially in those instances where the by-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. -In many cases when the compound is manufactured for purposes of demulsification,

.one is better off to obtain a polymer in the sense However. if

ramification, except in a previously described, 'particularly' a polymer whose molecular weight is a rather small multiple of the molecular weight "of the monomer, I for irist'ance'ya, polymer whose molecular weight is two,"three, four, live, or six times the molecular weight or the monomer. Polymerization is hastened by the'presence of an alkali, and thus,

in instances where it 'is necessary to have a maximu'm yield of the monomer, itmay be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be removed before; subsequent reaction. This, of course, can be done in any simple ma nner by conversion to sodium chloride, sodium sulfate, orany suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to l0, inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the effectiveness of the low multiple polymers as demulsifiers'. Previous reference has been made to thesfact that thecarboxylic hydrogen atom mightbe variously replacedby substituents, including organic radi cals, for instance, theradicals obtained from al- 0021013,: hydroxylated amines, nonhydroxylated aminespolyhydric alcohols, etc. Obviously, the reverseis also .true,.in that a free hydroxyl group may be, esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxy acetic acid, lactic acid; ricinoleic acid and also polybasic acids of thekind'herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as, to

polymerization, with the"; suggestion that byproducts or cogene'ric materials were formed, may be recapitulated with greater deilniteness, andlojne can'readily appreciate thatthe formation' of heat-rearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esterificationpolymers, or the heat-rearranged derivatives of the same, and thus including th'e heat-rearranged derivatives of both the polymers and ,esterification monomers, separately and jointly. Although the class of materials specifically contemplatedinthis instance is a comparatively small-andnarrow class of a broad genus, yet it isobviouslyimpossible to present any adequate formula which would cone template the present series in their complete manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, i e., -monomers' through sub-resinous 'pm mer m ble' products, 'water-emulsifi'able 7 oil s' or 'compounds, hydrctropic materialsbalsams, subresinous materials,- semi-resinous materials; andthe like, yet there is'always present the characteristic unitary hydrophile structure related back to'the oxyalkylation, particularly the oxyethylationjof the glycerol used as the raw material. Whefn'our new product is used as a demulsifier, in the resolution of oilfield emulsions, the demulsifier may in water in any ratio, and'a semi-resinous productapparenfly insoluble in water in ratios by which ordinary insoluble materials are characterized'm However; at such ratios the im msnae step. procedure.

must reside in interfacial position and the ability to usurp, preempt, or'replace the interfacial position previously occupied perhaps by :the emulsifying colloid. In any event, reviewedin this light, the obvious common property running through the entire series, notwithstandingvarriation in molecular size and physical make-up, .is absolutely apparent. Such statement is an obvious-oversimplification of the rationale underlying demulsification, and does not even consider the resistance of an interracial film to crumbling, displacement, being forced'into-solution, altered wetability, and the like. As to amidification polymers, for instance, where Z is a polyamino amide radical, see what is' said subsequently.

COMPLETED POLYMERIC DERIVATIVES memm' HEAT-REARRANGED C'oGENERs Example 1 A polyfunctional monomeric product of the kind described in Completed monomeric derivatives, Examples 1 to 7, preceding is heatedat approximately 220-240 C. with constant stirring, for a period of 2 to 60 hours, so as to elimin'ate suflicient water in order to insure that the resultant product has a molecular weight approximately twice that of the initial raw material.

COMPLETED POLYMERIC DERIVATI S INCLUDING HEAT-REARRANGED COGENERS Example 2 COMPL TED PoLYMERIc DERI ATIVES IxCLUnInc HEAT-REARRANGED COGENERS Example 3 7 The same procedure is followedas in Examples 1 and 2, preceding, except that one employs as monomeric reactants polyfunctional monomers selected from the type exemplified by Completed monomeric derivatives, Examples 8 to 10, inclusive.

.C oMPL ErEn POLYMERIC Dmnvarrvns INCLUDING.

HsAr-Rrsnesucrn Cocrmms Example 4 s The same procedure is followed'as in Examples 1 to 3, preceding, except that one polymerizes'a mixture instead of v a single monomer, for instance, a mixture of materials of the kind described, in Completed monomeric derivative, Example 3, and in Completed monomeric derivative, Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples. 1 1

It is understood, or course, that the polymerized product need not be obtainedas a result of a two- In other words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step. Indeed, the formation of the monomer and polymerization may take place simultaneously. This is especially; true if polymerization is conducted in the absence of a liquid'such as xylene-aspreviously described, and if one use a comparatively higher temperature,for instance, approximately 220": -C. for polymerization. Thus, one pound mole of an oxyethylated glycerol polymaleate of the kind described in previous examples, is mixed with one pound ,mole of a polyhydroxylated material of the kind described under the heading Hydroxylated diamide type intermediate, Ex-.

ample .10, and reacted for 20 hours at approximately 200 C. until the massis homogeneous. It is stirred constantly during reaction. Polyfunctionality .may'reside in dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be made in a single step, illustrates a phenomenon which sometimes occurs either insuch instances where alcoholic bodies of theikind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies .are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser degree, sufficientmonomeric materials so'that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous andexist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a heavier material, which is sticky'or'sub-resinous in nature. In many instances, it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.-

Materials of the kind herein contemplated may find uses as Wetting, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid I washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like, as'a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as 'germicides, insecticides, emulsifiersfor cosmetics, spray oils, waterrepellent textile finish, etc. These uses are by no means exhaustive.

However, the most important phase of the present invention, asfar as industrial application goes, is concerned with the use of the materials previously described as demulsifiers for Water-inoil emulsions, and more specifically, emulsions of .water or brine in crude petroleum.

We have found that the particular chemical compounds herein described may also be used for other purposes, for instance, as a break inducer in doctor treatment'of the kind intended to sweeten gasoline. '(See U. S. Patent No, 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbeanng strata by means'of strong mineral acid, such as hydrochloric acid. Similar1y,'some members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226,119, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension, depressants in combination with mineral acid or acidization of oil-bearing strata, reference is made to U. S. Patent ,No. 2,233,383, dated February 25, 1941, to De Groote and Keiser.

Cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds up reaction and polymerization, compared with a glass-lined vessel.

As has been previously indicated, the sub-genus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos, 497,118, 497,119, 497,120, 497,121, 497,122, 497,123, 497,124, 497,125, 497,126, 497,127, 497,128, 497,129, 497,130, 497,131, 497,132, 497,134 and 497,135, all filed August 2, 1943.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. The sub-resinous ester-linked acylated derivatives of a hydroxylated acylated diamide of in the acyl radical of a polycarboxy acid having not more than 6 carbon atoms and R3 is selected from the class consisting of hydrogen atoms, alkylol radicals, and esterified alkylol radicals, in which the acyl radical of the ester group is that of a detergent-forming monocarboxy acid having at least 8 carbon atoms and not more than 32 carbon atoms, and with the proviso that there shall be present at least one alcoholic hydroxyl radical and at least one of the aforementioned high molal monocarboxy acyl radicals; the acyl group substituted for a reactive hydroxyl hydrogen atom of said acylated diamide being the acyl radical of an acidic fractional ester of the formula:

in which -OCR1CO is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; Z represents a metallic cation; RO is a member of the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals and glycide radicals, and n represents a numeral varying from 3 to 10, and 12." represents a numeral varying from to 2, and n represents a numeral varying from 1 to 3, with the proviso that the sum of n"+n"=3.

2. The method of manufacturing esters, as defined in claim 1, which consists in esterifying a hydroxylated acylated diamide of the formula:

at least 8 carbon atoms and not more than 32 carbon atoms, and with the proviso that there shall be present at least one of the aforementioned high molal monocarboxy acyl radicals; with an acidic fractional ester of the formula:

in which --OCR1CO is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; Z represents a metallic cation; RO is a member of the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals and glycide radicals, and n represents a numeral varying from 3 to 10, and n" represents a numeral varying from 0 to 2; and n represents a numeral varying from 1 to 3, with the proviso that the sum of n"+n"'=3.

3. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms.

4. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms and at least one ethylene linkage.

5. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms and at least one ethylene linkage, and R is an ethylene radical.

6. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms and at least one ethylene linkage, R is an ethylene radical, and n is zero.

7. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms and at least one ethylene linkage, R is an ethylene radical, n" is zero, and the polycarboxy acid is dicarboxy.

8. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms and at least one ethylene linkage, R is an ethylene radical, 11." is zero, and OCR1CO is a maleic acid radical.

9. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms and at least one ethylene linkage, R is an ethylene radical, n is zero, and -OCR1CO is a phthalic acid radical.

10. The ester of claim 1, wherein the detergentforming monocarboxy acid radical is a higher fatty acid radical having 18 carbon atoms and at least one ethylene linkage, R is an ethylene radical, 1!. is zero, and OCR1CO is a succinic acid radical.

MELVIN DE GROOTE. BERNHARD KEISER. 

